Anthraquinone dyestuffs

ABSTRACT

The invention relates to new sulphonic acid group-containing anthraquinone dyestuffs of the general formula   IN WHICH A stands for an optionally substituted alkyl, cycloalkyl, alkylamine, cycloalkylamine, alkyloxy or cycloalkyloxy radical; for an optionally substituted, preferably sulphonated, arylamine or aryloxy radical; for an optionally substituted aralkyl, aralkylamine or aralkyloxy radical preferably sulphonated in the aromatic part; or for an amino group, Y represents a direct linkage or a bridge member, R1 to R5 denote, independently of one another, hydrogen, Halogen (Cl, Br, F), -NO2, -NH2, NH-alkyl, -NH-aryl, -NH-acyl, -Oalkyl, O-aryl, -OH, -S-alkyl, -S-aryl, -SO2NH-alkyl, SO2N(alkyl)2, -SO2NH-aryl, -SO2-alkyl, -SO2-aryl, -aryl. R1 may also stand for a lower alkyl radical, the radicals X denote sulphonic acid groups, p and p&#39;&#39; represent the number 1, 2 or 3, m denotes the number 0, 1 or 2, and n represents the number 0, 1 or 2, the sum total of m and n, in addition to the sulphonic acid groups which may be contained in the radical A, being at least 1.

llnited States Patent Machatzke et al.

[54] ANTHRAQUINONE DYESTUFFS [72] Inventors: Heinz Machatzke, Union, N.J.; Josef Singer, Leverkusen, Germany [73] Assignee: Farbenfabriken Bayer Aktiengesellschaft, Leverkusen, Germany [22] Filed: June 4, 1969 [21] Appl. No.: 830,524

[51] Int. Cl. ..C09b 1/52, C09b 1/56 [58] Field of Search ..260/372 [56] References Cited UNITED STATES PATENTS 3,519,656 7/1970 Schwander ..260/372 Primary Examiner-Lorraine A. Weinberger Assistant Examiner-E. Jane Skelly Attorney-Plumley & Tyner 5 7 ABSTRACT The invention relates to new sulphonic acid groupcontaining anthraquinone dyestuffs of the general formula 151 3,682,978 Aug. 8, 1972 R) r 0 R2 com 0 in which A stands for an optionally substituted alkyl, cycloalkyl, alkylamine, cycloalkylamine, alkyloxy or cycloalkyloxy radical; for an optionally substituted, preferably sulphonated, arylamine or aryloxy radical; for an optionally substituted aralkyl, aralkylamine or aralkyloxy radical preferably sulphonated in the aromatic part; or for an amino group,

Y represents a direct linkage or a bridge member,

R to R denote, independently of one another, hydrogen, Halogen (Cl, Br, F), -NO -NH NHalkyl, -NH-aryl, NH-acyl, Oalkyl, O-aryl, -OH, -Salkyl, Saryl, SO Nl-l alkyl, SO N(alkyl) --SO NH-aryl, SO alkyl, SO aryl, aryl.

R may also stand for a lower alkyl radical, the radicals X denote sulphonic acid groups, p and p represent the number I, 2 or 3, m denotes the number 0, l or 2, and n represents the number 0, 1 or 2, the sum total of m and n, in addition to the sulphonic acid groups which may be contained in the radical A, being at least 1.

10 Claims, No Drawings ANTHRAQUINONE DYESTUFFS The invention relates to new sulphonic acid groupcontaining anthraquinone dyestuffs of the general formula in which A stands for an optionally substituted alkyl, cycloalkyl, alkylamine, cycloalkylamine, alkyloxy or cycloalkyloxy radical;

for an optionally substituted, preferably sulphonated,

arylamine or aryloxy radical;

for an optionally substituted aralkyl, aralkylamine or aralkyloxy radical preferably sulphonated in the aromatic part; or for an amino group,

Y represents a direct linkage or a bridge member,

R to R denote, independently of one another, hydrogen, Halogen (Cl, Br, F), NO Nl-l NH-alkyl, -NH-aryl, Nl-l-acyl, -O-alkyl, Oaryl, OH, S-alkyl, S-aryl, SO NH-alkyl, -SO N(alkyl) SO Nl-laryl, SO -alkyl, SO aryl, aryl.

R, may also stand for a lower alkyl radical, the radicals X denote sulphonic acid groups, p and p represent the number 1, 2 or 3, m denotes the number 0, l or 2, and n represents the number 0, l or 2, the sum total of m and n, in addition to the sulphonic acid groups which may be contained in the radical A, being at least 1.

For the radical A the following individual examples may be mentioned:

for the optionally substituted alkyl radical: straightchain or branched alkyl radicals with one to 12, preferably with one to seven, carbon atoms; as well as cycloalkyl radicals with preferably five or six carbon atoms; these radicals may also contain multiple bonds; for the optionally substituted alkylamine or alkyloxy radical those with one to 12, preferably one to eight,

carbon atoms in the straight-chain or branched carbon chain which may also be unsaturated; as well as cycloalkylamine radicals with preferably five or six car- 5 bon atoms, these radicals may also contain multiple bonds; for the optionally substituted, preferably sulphonated, arylamine or aryloxy radical: a monoor polycyclic radical, such as a radical of the benzene, naphthalene, diphenyl and the diphenyl-methane series; for the optionally substituted, preferably sulphonated, aralkyl, aralkylamine or aralkyloxy radical those which contain in the aromatic part the afore-mentioned monoand polycyclic radicals, and in the aliphatic part one to 12, preferably one to seven, carbon atoms, the aliphatic part possibly also containing multiple bonds.

The radicals mentioned for A and also those mentioned for R to R which are suitable for a substitution, may carry further substitutents, e.g. alkyl radicals with one to four carbon atoms; halogen atoms, such as fluorine, chlorine or bromine; nitro, cyano and hydroxy and groups; alkoxy groups with preferably one to four carbon atoms; a cycloalkyloxy radical with preferably five or six carbon atoms; an optionally substituted phenoxy radical (substituents are preferably halogen, such as fluorine, chlorine, bromine; C, 4 alkyl or alkoxy radicals, cyano, nitro, SO l-l or carboxyl groups); lower alkylsulphonyl groups, arylsulphonyl, preferably phenylsulphonyl, groups, trifluoromethyl radicals, carboxylic acid and sulphonic acid groups as well as their esters, preferably C C alkyl esters, the alkyl groups of which may carry one or more substituents, preferably hydroxy and lower alkoxy radicals; amino groups, monoor dialkyl-amino groups each containing one to four carbon atoms, cycloalkylamino groups (preferably containing five or six carbon atoms), arylamino groups, the aryl radical preferably being a phenyl group which may be substituted by one or more halogen atoms, such as fluorine, chlorine or bromine, furthermore by C, alkyl or alkoxy radicals, cyano, nitro, sulphonic acid or carboxyl groups; acylarnino groups, especially those with aliphatic or optionally substituted aromatic acyl radicals, such as acetyl, propionyl, benzoyl, lower alkylsulphonyl radicals or phenylsulphonyl radicals; alkyl thioether radicals or optionally substituted phenyl thioether radicals; optionally substituted carboxamide or sulphonamide groups as well as acylated sulphonamide groups, such as the disulphimide group.

Examples for the bridge member Y are the following: an O or S atom, the groups NH, NH-alkylene--, Oalkylene, --Salkylene-, CONH-, CONl-lalkylene, SO -NH, SO O, SO NH-alkylene--, OalkyleneO-, O-alkylene-S-, Oalkylene-NH-, --S-alkylene-S -Salkylene--NH-, NHalkyleneNH-, the alkylene chains possibly being interrupted by one or more hetero atoms and containing up to l2 carbon atoms, and the above-mentioned alkyl, acyl and aryl radicals possibly carrying further substituents.

Among the radicals mentioned for R to R the radical R, can obviously also be the radical CHzNH o o A in which A, R X, p and m have the same meaning as above.

The new anthraquinone dyestuffs are obtained by various methods of preparation.

1. Anthraquinone dyestuffs of the formulae (III) in which n, p, p, X, Y and R to R have the same meaning as that given for the formula (I), are condensed in the right-hand side of the phenyl nucleus with methylol amides of the formula HOCH -NHCOA v in which A has the same meaning as that given for the formula (I), or with functional derivatives of those methylol amides which are capable of reacting in the same way as the methylol amides, with the formation of dyestuffs of the formula (I), for example, in the presence of strong acids, for example, 80 to 100 percent sulphuric acid, 80 to 100 percent phosphoric acid, or acetic acid/hydrochloric acid mixtures.

3. Anthraquinone compounds of the formula R2 OW ll l V g H R: 4

in which X, R R R and R n and p have the same meaning as that given for the formula (I), and V represents a splittable group, for example, and in particular, an aryloxy group, such as the phenyloxy group, or a halogen atom, e.g. Br, are condensed with derivatives of the formula ClhNllCOA (VII) in which R,, p, X, m, A and Y have the same meaning as that given for the formula (I), with the splitting off of V-H and with the formation of dyestuffs of the formula (I). For this purpose the compounds Vl, preferably with an excess of compounds (Vll), can be condensed in an alkaline, organic or organic/aqueous or aqueous medium at an elevated temperature, eg at temperatures of about 80 150 C.

The new anthraquinone dyestuffs (I) contain by definition at least one sulphonic acid group in the anthraquinone nucleus and/or in the phenyl nucleus. This water-solubilizing substituent is, as explained above, introduced into the dyestuffs in such a manner that it is present in the anthraquinone compound used as reaction component or, advantageously, introduced by sulphonation only during or after the condensation reaction. If the sulphonic acid group is already contained in the radical A before the condensation according to the method of production (2) or (3), then the additional sulphonation can be omitted.

Examples of suitable anthraquinone starting compounds (II) or III) are the following H) on Go-Q-om-mtc o-om-cm-cm-on II 0 OH r vm c1 /\O-CH2-NHCONH ll 0 6H 0 NH: ll 1 ws onfimboozm H Y 0 OH O NH: CH3 H l I I OCH2CH2CH2O CHa ll l 0 OH (I) CHz-NH-C-NI-ICHa 7 8 Examples of the methylolamides of the fOfmula The parts in the following examples are parts by or derivatives reacting in the same way are inter alia: 7 weight; the temperatures are given as degrees cen- O tigrade. HOCH Z\'H-y CHzCH -CH -CH HO-CH;NH 5

co-cwmu, HO-CHzNHC O-CnHzni-1 EXAMPLE 1 (=7 to 9; coconut oleic acid first runnings) A solution of 80 parts l-amino-4-hydroxy-2-phenoxy v anthraquinone in 800 parts 97 percent sulphuric acid is HO CH2 IHCO CHM HO CHZ NH*CO H m slowly mixed at 5 to 10 with 65 parts N-methoxymethyl-N-2-ethyl-hexyl-urea. The temperature is maintained at until the anthraquinone deriva- CH3 O CH1 NH COC4H tive is completely converted. The reaction mass is then 0 poured on to ice, the product filtered off with suction P; 1 5 and washed with water until neutral and dried.

- The resultant dyestuff is sulphonated in usual CHsO-CH -NHC O-NH@ manner at 20 with 20 percent oleum and, after pouring on to ice and salting out with common salts, isolated. The yield amounts to 140 parts of the dyestuff of the (U) TH; $03 ll o -cm-Nir-c0xncii,-r:nc1i, t -n1 I l o 011 9 2 30 It dyes polyamide fibers and wool from an acidic and CH OCH XHC-NHCIICll;-CII *SO3II neutral bath in bluish red shades of very good fastness CH3 properties.

CnPct/i In the procedure is followed as indicated above, but replacing the methoxymethyl-ethylhexyl-urea by 0 CH2 f equivalent quantities of the following methylol or c1r,o-cIi -X-CNHCI C :CHZ 1 3 methoxymethyl compounds: N-methylol-chloro-aceta- 1 a O mide, N-methylol-isobutyl-acetamide, N-methylol- Q a dodecane acid amide, the N-methylol derivative of the 01130 c 2 amides of coconut oleic acid(C -C )first runnings, N- Examples of suitable anthraquinone compounds 40 F 9 f N'methoxymethyl'? (VI) are inter alia: p-mtrophenyl-propiomc acid amide, N-methylol .o z bromo 4 hydroxy amhraquinone urethane, N-hydroxymethyl-carbamic acid methyl 2,44" ibromeamhraquinone, l4 dihydroxy 2 bromo ester, methylol urea, N-methoxymethyl-N -methylanthraquinone, 1 amino z phenoxy 4 hydmxy urea, N-methoxymethyl-N'-cyclohexyl-urea, N,N'-bisanthr quinone, l-amino-2-(2'-chlorophenoxy)-4- methylol urea, Y Y W y hydroxy-anthraquinone, l,4-diamino-2,3-dichloro- YPmPYn'urea N'methoxymethyl'N anthraquinone, l,4-diamino-2-phenoxy-3-chloro- P PyU' y hy "p' ly p anthraquinone, l,4-diarnino-2-phenoxy-anthraquinylbenzyl'urea, y -pl p y one-3-sulphonic acid, 1,4-diamino-anthraquinone-2- Y D' y y -p' p sulphonic acid chloride, l,4 diamino-anthraquinone-2- y -w))-ur then red dyestuffs are also carboxylic acid chloride, l-amino-2,5-dibromo-4- Obtained with good fastness Propertieshydroxy-anthraquinone, l,4-diamino-2,3,5,8- If l-amino-4-hydroxy-2-phenoxy-anthraquinone is tetrachloro-anthraquinone. replaced by the equivalent quantity of 5-chloro-l- The new dyestuffs are especially suitable for the dyeamino-4-hydroxy-2-phenoxy-anthraquinone, then ing and printing of nitrogen-containing fibers and there is obtained by the same. method of operation the fabrics, particularly of wool and synthetic polyamides. dyestuff of the constitution Cl 0 )H The dyeings are especially distinguished by very good It also dyes polyamide fibers in bluish red shades with fastness to light. good fastness properties.

3,682,978 9 l EXAMPLE 2 are obtained which dyes synthetic superpolyarnide Sixteen p LaminoAMdroxrLPhenoxy; fibers and wool in red-violet shades with good fastness anthr uinone and 13 arts N-meth th I b propenm' i aciifimnitmbenzyl :ster are gm ff iz Valuable-red-vlolet dyestuffs result likewise when the procedure is followed as described in Exam 1 3 120 parts 96 percent sulphurlc acid, and the mixture p e kept at 20 until the reaction is completed. Sixty parts but replacing the methoxymemyl urea there used by 65 percent oleum are then added, while cooling, and gg igif aggf gf i zg jgfiglz f g i? comlhe mixture is Poured to ice, after complete water N-me'thoxymethyl-carbamic acid-4-r l itrob enz l e122? solubility is achieved, the product is filtered off with N methoxymethyl pmpionic acid 8mm y suction and washed with water containing common salt,until neutral. The resultant dyestufi' has the COnm stitution Twenty-two parts l-amino-4-p-toluido-2-pl1enylmer- I! will; H m" OQH lt dyes wool and synthetic polyamide fibers from an capto-anthraquinone and 5 parts methylol urea are disacidic and neutral bath in bluish red shades which are solved at 0 5 in 120 parts 96 percent sulphuric acid particularly fast to wet processing. 25 and the mixture is then warmed up to room tempera- When the nitro group of the above dyestuff is ture. One-hundred parts 65 percent oleum are added reduced to the amino group and the latter acylated, a after hours, while cooling, and the temperature is dyestuff can be obtained by an additional treatment maintained at 20 for a further 5 hours. The mixwith oleum,which has an improved solubility and the ture is then poured on to ice, the product filtered off same shade. with suction, washed with a dilute common salt solu- When the equivalent quantity of N-methoxymethyltion until neutral and dried. The resultant dyestufi has carbamic acid-6-p-nitrophenyl-3methylhexyl (4)- orthe Const tution N-methoxymethyl-carbamic acid-isononylor 2,2- dimethyloctylor 2,2-dimethyldecyl-ester is used, in-

l stead of the corresponding nitrobenzyl ester mentioned in the first paragraph of this example, dyestuffs are ob- I tained which dye wool and synthetic polyamide fibers SOaH o12rrNH-00NHe in bluish red shades which are also very fast to wet processing.

EXAMPLE3 e lt dyes synthetic polyamide fibers and wool in fast,

Twenty-one parts l,4-diamino-2,3-diphenoxygreenish blue Shades anthraquinone are introduced at a temperature of 0 5 into 150 parts 96 percent sulphuric acid followed by EXAMPLE 5 the addition at 0 15 of 20 parts N-methoxymethyl- N'-ethyl urea. The mixture is stirred at 20 for 20 hours, then cooled to 0 and 100 parts 65 oleum are run in. The mixture is stirred at 20 25 for a further 5 00 into 200 ans 96 ercem Sul hufic acid. The hour? pourFd on to 9 parts The ture is stirrer at 20 25 for 20 ours and then poured preclpltated dyestufi rs filtered off with suction, washed on to 3,000 parts of The precipitated dyesmfi is first w water w a "2 P f common tered oif with suction, washed first with water, then solutlon and finally 17 49 Parts of the with a 5 l0 percent common salt solution until ap- Forty-one parts l,4-diamino-2-phenoxy-anthraquinone-3-sulphonic acid and 35 parts N-methoxymethyl- N'-(4-phenyl-sulphonyl-phenyl)-urea are introduced at dyestuff ofthe constitufion 55 proximately neutral and dried at 70. The dyestuff of the constitution nors GHrNH-C0-NHCzHr NH; O

(\ -sotrr U i i 0 0 Nil,

is obtained which dyes synthetic polyamide fibers in llolsoil2 Nil-coNil-01m and wet processing.

blue-violet shades which have a good fastness to light Fifty parts of the dyestuff of the above formula are introduced at 20 25 into 200 parts 10 percent oleum and the mixture is stirred at the same temperature for 4 5 hours. it is then poured on to ice, the precipitated dyestuff is filtered off with suction and washed until neutral with a percent common salt solution. The dyestufi' of the constitution SOsH EXAMPLE 6 Ninety parts 1-amino-2-phenoxy-4-hydroxyanthraquinone, 500 parts N-4-(B-hydroxyethyl)- benzyl-N'-benzyl-urea and parts potassium hydroxide are heated at 140 150 for 10 hours. The mixture is allowed to cool, poured into water and the product is filtered off with suction. The latter is recrystallized from pyridine and dried. The dry dyestuff is introduced into 250 parts 30 percent oleum and the mixture stirred at 20 for 5 hours. The mixture is poured on to 5,000 parts of ice, the product is filtered off with suction and washed with water and a common salt solution. After drying, the dyestuff of the constitution is obtained which dyes synthetic polyamide fibers in red shades of good fastness to light and washing.

EXAMPLE 7 ture is subsequently poured on to 5,000 parts of ice, the

precipitated dyestufi is filtered off with suction, washed first with water, then with a 5 10 percent common salt solution, and 43 parts of the dyestuff of the constitution 2 (I) OH S0311 OCHg are obtained, which dyes synthetic polyamide fibers in blue shades which are fast to light.

EXAMPLE 8 Four parts of the dyestuff obtained according to Example l are introduced into a dyebath of 2,000 parts of water containing 10 parts ammonium acetate, 4 parts glacial acetic acid and parts of a synthetic polyamide fiber hank. The bath is slowly heated to boiling within 30 minutes, and the dyestuff is allowed to draw onto the fiber at boiling temperature in the course of 1 hour. An intense bluish red dyeing is obtained which is especially distinguished by a very good fastness to light.

EXAMPLE 9 We claim: l Anthraquinone dyestuff of the formula R O 5) H I in which Y is O, -S-, Oalkylene, or 0 alkylene 0-; where alkylene is CH Cl-l CH- CH CH CH or cn cn cn cu A is selected from the group consisting of amino;

alkylamino with one to 12 carbon atoms in the straight chain or branched carbon chain which may also be unsaturated cycloalkylamino with five or six carbon atoms which may contain multiple bonds arylamino radical of the benzene, naphthalene, diphenyl or diphenyl-methane series;

aralkylamino radical which contains in the aromatic part the afore-mentioned aryl radicals and in the aliphatic part one to 12 carbon atoms wherein the aliphatic part may contain multiple bonds and one of the said radicals A which carries further substituents selected from the group consisting of alkyl with one to four carbon atoms; halogen; nitro; cyano; hydroxy; alkoxy with one to four carbon atoms; cycloalkyloxy with five or six carbon atoms; phenoxy; phenoxy substituted by halogen, C, alkyl, C alkoxy, cyano, nitro, SO H-- or carboxy; lower alkylsulphonyl groups; phenylsulphonyl; trifloromethyl; carboxylic acid or sulphonic acid groups or their C, C alkyl esters wherein the alkyl groups may carry one or more substituents of the class hydroxy and lower alkoxy; arnino; monoor dialkyl-amino containing one to four carbon atoms in the alkyl chain; cycloalkylamino containing five or six carbon atoms; phenyl amino; substituted phenyl amino containing one or more halogen atoms, C alkyl, C alkoxy, cyano, nitro sulphonic acid or carboxyl groups; acylamino where acyl is selected from the class acetyl, propionyl, benzoyl, lower alkylsulphonyl and phenylsulphonyl; phenyl thioether; carboxarnide; sulphonamide; and disulphimide, R R R and R are selected from the group consisting of H, Halogen, N NH OH or NH alkyl containing one to four carbon atoms NH phenyl NH acyl where acyl is acetyl, benzoyl, phenylsulfonyl 0 alkyl containing one to four carbon atoms 0 phenyl S alkyl containing one to four carbon atoms S phenyl SO phenyl phenyl one of said radicals R R R or R, which carries, in the alkyl, phenyl, further substituents selected from the group consisting of alkyl with one to four carbon atoms; halogen; nitro; cyano; hydroxy; alkoxy with one to four carbon atoms; cycloalkyloxy with five or six carbon atoms; phenoxy; phenoxy substituted by halogen, C,.., alkyl, C alkoxy; cyano, nitro, SO H or carboxy; lower alkylsulphonyl groups; phenylsulphonyl; trifluoromethyl; carboxylic acid or sulphonic acid groups or their C C alkyl esters wherein the alkyl groups may carry one or more substitutents of the class hydroxy and lower alkoxy; amino; monoor dialkylamino containing one to four carbon atoms in the alkyl chain; cycloalkylamino containing five or six carbon atoms; phenyl amino; substituted phenyl amino containing one or more halogen atoms, C alkyl, C, alkoxy, cyano, nitro, sulphonic acid or carboxyl groups; acylamino where acyl is selected from the class acetyl, propionyl, benzoyl, lower alkylsulphonyl and phenylsulphonyl; phenyl thioether; carboxamide; sulphonamide; and disulphimide, and wherein R can be a lower alkyl radical N(CH or SO NH X is SO H pandp' are 1,2,or3

and m and n are 0,1, or 2; the sum ofm and n in addition to any SO H group in A being at least 1. 2. Anthraquinone dyestuff of the formula (Rm (Run in which A is selected from the group consisting of amino; alkylamino with one to 12 carbon atoms in the straight chain or branched carbon chain which may also be unsaturated; cycloalkylamino with five or six carbon atoms which may contain multiple bonds arylamino radical of the benzene, naphthalene, diphenyl or diphenyl-methane series; aralkylamino radical which contains in the aromatic part the afore-mentioned aryl radicals and in the aliphatic part 1 to 12 carbon atoms wherein the aliphatic part may contain multiple bonds and one of the said radicals A which carries further substituents selected from the group consisting of alkyl with one to four carbon atoms; halogen; nitro; cyano; hydroxy; alkoxy with one to four carbon atoms; cycloalkyloxy with five or six carbon atoms; phenoxy; phenoxy substituted by halogen, C, alkyl, C, alkoxy, cyano, nitro, SO H- or carboxy; lower alkylsulphonyl groups; phenylsulphonyl; trifluoromethyl; carboxylic acid or sulphonic acid groups or their C C alkyl esters wherein the alkyl groups may carry one or more substitutents of the class hydroxy and lower alkoxy; amino; monoor dialkyl-amino containing one to four carbon atoms in the alkyl chain; cycloalkylamino containing five or six carbon atoms; phenyl amino; substituted phenyl amino containing one or more halogen atoms, C, alkyl, C, alkoxy, cyano, nitro, sulphonic acid or carboxyl groups; acylamino where acyl is selected from the class acetyl, propionyl, benzoyl, lower alkylsulphonyl and phenylsulphonyl; phenyl thioether; carboxamide; sulphonamide; and disulphimide, R R R and R are selected from the group consisting of H, Halogen, NO NH OH or NH alkyl containing one to four carbon atoms NH phenyl NH acyl where acyl is acetyl, benzoyl, phenylsulfonyl 0 alkyl containing one to four carbon atoms 0 phenyl S alkyl containing one to four carbon atoms S phenyl SO phenyl phenyl one of said radicals R,, R R or R, which carries, in the alkyl, phenyl, further substituents selected from the group consisting of alkyl with one to four carbon atoms; halogen; nitro; cyano; hydroxy; alkoxy with one to four carbon atoms; cycloalkyloxy with five or six carbon atoms; phenoxy; phenoxy substituted by halogen, C alkyl, C, alkoxy, cyano, nitro, SO H or carboxy; lower alkylsulphonyl groups; phenylsulphonyl; trifluoromethyl; carboxylic acid or sulphonic acid groups or their C C alkyl esters wherein the alkyl groups may carry one or more substituents of the class hydroxy and lower alkoxy; amino; monoor dialkyl-amino containing one to four carbon atoms in the alkyl chain; cycloalkylamino containing five or six carbon atoms; phenyl amino; substituted phenyl amino containing one or more halogen atoms, C, alkyl, C, alkoxy, cyano, nitro, sulphonic acid or carboxyl groups;

acylamino where acyl is selected from the class 6. The anthraquinone dyestufi of claim 1 having the acetyl, propionyl, benzoyl, lower alkylsulphonyl formula and phenylsulphonyl; phenyl thioether; carboxamide; sulphonamide; and disulphimide, and wherein R can be a lower alkyl radical N(CH or SO NH X is SO l-l pandp' are 1,2,or3

and m and n are 0, l, or 2; the sum ofm andn in addition to any SO H group in A being at least 1.

3. Dyestufi of claim 2 where A is NH NH alkyl with one to eight carbons and NH alkyl with one to eight carbons and a substituent s om O NH: of the class nitrophenyl, methoxy, sulfophenyl, A O phenyl, hydroxy, methylsulfonylphenyl and, phen- Q l N11: S0 5 IAG Q 7. The anthraquinone dyestuff of claim 1 having the formula yl sulfonyl phenyl, NH cyclohexyl, NH phenyl and NH phenyl with a substituent of the class phenyl sulfonyl and methylsulfonyl R1 is H, Cl, Br, NHg, NHCH3, NHC4H9, NHC2H4OH,

N(CH3)2 NHCBHM NHCOOHa, NHCOCGHM 8. The anthraquinone dyestuff of claim 1 having the SO2c6H5, OH, OCH OC H ()C H oc so formula SCH3, SC4H9 s s s, SOgNH SO NHC H OH, ITIH: 0 11 ji szggCsHCi SOzCeHm SOzCzHS, C1 alkyl S CH2 NH O O NH2 R iS NH OH,

4 is OH, NH V I l NII @cm substituted by one or more members of the class 9. The anthraquinone dyestufl of claim 1 having the Cl, Br, NH NHCH NHC H NHC H OH, N(CH formula NHCsHs, NHCOC6H5, NHSOgCsHs, NH O so c n OH, 0on 00m n T oc u oc u so n, son sc n sc n SO2NH2, 0 H SO2NHC2HC4OH, so uucauou, somuc n cm so 9 a 0 .,alkyl or is Br 40 V -s 03 R5 is H, OH, N02, Br, NH 01, p is 0-2. (5 IL" 4. The anthraquinone dyestuff of claim 1 having the formula 5. The anthraquinone dyestufi of claim 1 having the 10. The anthraquinone dyestufi of claim 1 having the formula formula (I) IIIHZ S 03H 5 5 fi N112 A 0-- o o 1-I,o H

ll 0 OH 0 

2. Anthraquinone dyestuff of the formula
 3. Dyestuff of claim 2 where A is NH2 NH alkyl with one to eight carbons and NH alkyl with one to eight carbons and a substituent of the class nitrophenyl, methoxy, sulfophenyl, phenyl, hydroxy, methylsulfonylphenyl and, phenyl sulfonyl phenyl, NH cyclohexyl, NH phenyl and NH phenyl with a substituent of the class phenyl sulfonyl and methylsulfonyl R1 is H, Cl, Br, NH2, NHCH3, NHC4H9, NHC2H4OH, N(CH3)2, NHC6H5, NHCOOH3, NHCOC6H5, NHSO2C6H5, OH, OCH3, OC4H9, OC6H5, OC6H9SO3H, SCH3, SC4H9, SC6H5, SO2NH2, SO2NHC2H4OH, SO2NHC6H5, SO2C6H5, SO2C2H5, C1 4 alkyl p is 0-2 R2 is NH2, OH, R4 is OH, NH2 substituted by one or more members of the class Cl, Br, NH2, NHCH3, NHC4H9, NHC2H4OH, N(CH3)2, NHC6H5, NHCOOH3, NHCOC6H5, NHSO2C6H5, NHSO2C6H5, OH, OCH3, OC4H9, OC6H5, OC6H9SO3H, SCH3, SC4H9, SC6H5, SO2NH2, SO2NHC2H4OH, SO2NHC2H4OH, SO2NHC6H5, SO2C6H5, SO2C2H5, C1 4 alkyl or is Br R5 is H, OH, NO2, Br, NH2, Cl, p'' is 0-2.
 4. The anthraquinone dyestuff of claim 1 having the formula
 5. The anthraquinone dyestuff of claim 1 having the formula
 6. The anthraquinone dyestuff of claim 1 having the formula
 7. The anthraquinone dyestuff of claim 1 having the formula
 8. The anthraquinone dyestuff of claim 1 having the formula
 9. The anthraquinone dyestuff of claim 1 having the formula
 10. The anthraquinone dyestuff of claim 1 having the formula 